An implementation of the relativistic multireference Fock-space coupled cluster method is presented which allows simultaneous calculation of potential surfaces for different oxidation states and electronic levels of a molecule, yielding values for spectroscopic constants and transition energies. The method is tested in pilot calculations on the and HgH molecules, and is shown to give a good and balanced description of various electronic states and energies.
REFERENCES
1.
L.
Visscher
, T. J.
Lee
, and K. G.
Dyall
, J. Chem. Phys.
105
, 8769
(1996
).2.
L.
Visscher
, O.
Visser
, P. J. C.
Aerts
, H.
Merenga
, and W. C.
Nieuwpoort
, Comput. Phys. Commun.
81
, 120
(1994
).3.
L.
Visscher
, J.
Styszinski
, and W. C.
Nieuwpoort
, J. Chem. Phys.
105
, 1987
(1996
);W. A.
De Jong
, L.
Visscher
, and W. C.
Nieuwpoort
, J. Chem. Phys.
107
, 9046
(1997
);W. A.
De Jong
, J.
Styszynski
, L.
Visscher
, and W. C.
Nieuwpoort
, J. Chem. Phys.
108
, 5177
(1998
).4.
For a review of multireference CC methods see
D.
Mukherjee
and S.
Pal
, Adv. Quantum Chem.
20
, 292
(1989
).5.
I. Lindgren and J. Morrison, Atomic Many-Body Theory, 2nd ed. (Springer, Berlin, 1986).
6.
For a review of nonrelativistic FSCC applications see
U.
Kaldor
, Theor. Chim. Acta
80
, 427
(1991
).7.
U.
Kaldor
, in Recent Progress in Many-Body Theories, edited by E. Schachinger, H. Mitter, and M. Sormann (Plenum, New York, 1995), Vol. 4, p. 135;Y. Ishikawa and U. Kaldor, in Computational Chemistry: Review of Current Trends, edited by J. Leszczynski (World Scientific, Singapore, 1996), Vol. 1, p. 1;
U. Kaldor, in Recent Advances in Coupled-Cluster Methods, edited by R. J. Bartlett (World Scientific, Singapore, 1997), p. 125;
8.
9.
M.
Seth
, P.
Schwerdtfeger
, M.
Dolg
, K.
Faegri
, B. A.
Hess
, and U.
Kaldor
, Chem. Phys. Lett.
250
, 461
(1996
).10.
11.
12.
E.
Eliav
, U.
Kaldor
, and B. A.
Hess
, J. Chem. Phys.
108
, 3409
(1998
).13.
A.
Landau
, E.
Eliav
, Y.
Ishikawa
, and U.
Kaldor
, J. Chem. Phys.
114
, 2977
(2001
).14.
DIRAC, a relativistic ab initio electronic structure program, Release 3.2 (2000), written by T. Saue, V. Bakken, T. Enevoldsen, T. Helgaker, H. J. Aa. Jensen, J. K. Laerdahl, K. Ruud, J. Thyssen, and L. Visscher (http://dirac.chem.sdu.dk).
15.
J. Paldus, in Relativistic and Electron Correlation Effects in Molecules and Solids, edited by G. L. Malli (Plenum, New York, 1994), p. 207.
16.
17.
18.
19.
20.
21.
W. A.
de Jong
, L.
Visscher
, and W. C.
Nieuwpoort
, J. Chem. Phys.
107
, 9046
(1997
).22.
23.
24.
R. J. Le Roy, LEVEL 7.4: A computer program for solving the radial Schrödinger equation for bound and quasibound levels. University of Waterloo Chemical Physics Research Report No. CP-642R, 2001 (http://leroy.uwaterloo.ca).
25.
M. T.
Zanni
, T. R.
Taylor
, B. J.
Greenblatt
, B.
Soep
, and D. M.
Neumark
, J. Chem. Phys.
107
, 7613
(1997
).26.
J.
Vala
, R.
Kosloff
, and J. N.
Harvey
, J. Chem. Phys.
114
, 7413
(2001
).27.
M. T.
Zanni
, V. S.
Batista
, B. J.
Greenblatt
, W. H.
Miller
, and D. M.
Neumark
, J. Chem. Phys.
110
, 3748
(1999
).28.
L. B.
Knight
, Jr., and W.
Weltner
, Jr., J. Chem. Phys.
55
, 2061
(1971
).29.
30.
31.
J.
Dufayard
, B.
Majournat
, and O.
Nedelec
, Chem. Phys.
128
, 537
(1988
).32.
P. J.
Hay
, W. R.
Wadt
, L. R.
Kahn
, and F. W.
Bobrowicz
, J. Chem. Phys.
69
, 984
(1978
).33.
U.
Häussermann
, M.
Dolg
, J.
Stoll
, H.
Preuss
, P.
Schwerdtfeger
, and R. M.
Pitzer
, Mol. Phys.
78
, 1211
(1993
).34.
A. B.
Alekseyev
, H.-P.
Liebermann
, R. J.
Buenker
, and G.
Hirsch
, J. Chem. Phys.
104
, 4672
(1996
).35.
N. S.
Mosyagin
, A. V.
Titov
, E.
Eliav
, and U.
Kaldor
, J. Chem. Phys.
115
, 2007
(2001
).36.
G. Herzberg, Molecular Spectra and Molecular Structure. I. Spectra of Diatomic Molecules (Van Nostrand Reinhold, New York, 1950).
37.
38.
L.
Visscher
, T.
Saue
, and J.
Oddershede
, Chem. Phys. Lett.
274
, 181
(1997
).39.
The H basis is the relativistically recontracted aug-cc-PVTZ basis of
T. H.
Dunning
, Jr., J. Chem. Phys.
90
, 1007
(1989
).40.
M.
Gutowski
, J. H.
Van Lenthe
, J.
Verbeek
, F. B.
Van Duijneveldt
, and G.
Chalasinski
, Chem. Phys. Lett.
124
, 370
(1986
);41.
K. P. Huber and G. Herzberg, Molecular Spectra and Molecular Structure. IV. Constants of Diatomic Molecules (Van Nostrand Reinhold, New York, 1979).
42.
43.
M. C. R.
Cockett
, R. J.
Donovan
, and K. P.
Lawley
, J. Chem. Phys.
105
, 3347
(1996
).44.
45.
This content is only available via PDF.
© 2001 American Institute of Physics.
2001
American Institute of Physics
You do not currently have access to this content.